Lead-free solders such as SnAg and SnAgCu are used extensively as replacements of SnPb solders in microelectronics packaging. But these alloys have several drawbacks, such as poor wetting ability and formation of intermetallic compounds (IMC). Doping of rare earth element (RE) on SnAg alloys has been found to improve the wetting property, reduce IMCs and their growth, and refine the microstructure which results in improved mechanical properties of the solder. This study focuses on establishing the quantitative effects of RE doping on the microstructure and mechanical behavior of 96.5Sn3.5Ag alloy. SnAg alloys with different amounts of Lanthanum were made. Specimens were cast under typical reflow conditions, and then aged at different temperatures for three different aging times. Quantitative microscopy was conducted on samples with different amounts of La doping. It was found that doping greatly reduces the grain size, as well as the size of the intermetallic particles Ag3Sn. However, the inter-particle spacing remains relatively unaffected by the La doping amount. Creep tests at various temperatures and strain rates were conducted. The results show that La doping increases creep resistance of the SnAg alloy by ~15%. The creep test result can be fit into a modified microstructure dependent Anand model. A new constitutive law was also proposed to account for the hierarchal microstructure over multiple length scales. Specifically, at the sub micrometer scale, the SnAg eutectic region is treated as a particulate-reinforced composite with the Ag3Sn being the particle and Sn being the matrix. At the micrometer length scale, the solder alloys is treated as a two-phase composite with the Sn dendrite as the particle and the SnAg eutectic region as the matrix. Good agreement was found between the model predictions and the creep test results. Fatigue test was performed on bulk samples. It was found that RE doping increases the fatigue life of SnAg alloy by a factor of 5.

Laseres de estado sólido que operan en la región espectral de seguridad ocular alrededor de los 2 micrómetros (2µm) son de elevado interés en la actualidad debido a su potencial aplicación en los campos de la medicina, teledetección remota y como fuentes de bombeo en osciladores ópticos paramétricos (OPOs) para conversión en el infrarrojo medio. La transición láser en las 2 µm es posible en los iones de tulio (Tm) ligeramente por debajo de las 2 µm y en iones de holmio (Ho) ligeramente por encima de las 2 µm. La generación láser en iones de Tm es relativamente simple con la utilización de láseres de diodo como fuentes de bombeo, sin embargo, los láseres basados en Ho se han conseguido tradicionalmente en el pasado mediante el codopaje con Tm o mediante bombeo directo del nivel emisor del Ho. Recientemente, diodos láser que operan a 1.9 µm han aparecido en el mercado con buena eficiencia y con alto potencial para el escalado en potencia de los láseres de Ho. Los láseres de Ho son más apropiados que los láseres de Tm especialmente para aplicaciones médicas por dos razones: La longitud de onda láser ligeramente por encima de las 2 µm, donde el agua (mayor componente del cuerpo humano) presenta una ligera menor absorción que la típica longitud de onda láser del Tm, hace que el láser penetre más en el tejido humano. La segunda razón es que los láseres de Ho pueden operar en régimen pulsado generando mayores energías por pulso que los láseres de Tm debido al mayor tiempo de vida del nivel emisor 5I7 y las aplicaciones médicas requieren por lo general régimen pulsado para evitar daño térmico del tejido. Numerosos óxidos y fluoruros cristalinos han demostrado ser adecuadas matrices para Ho, sin embargo, poca atención se ha puesto en los dobles tungstatos cristalinos de fase monoclínica, de fórmula química KRE(WO4)2, brevemente KREW, donde RE = Y, Gd y Lu conocidos por ser matrices láser muy eficientes para la generación láser a potencias intermedias. Estos cristales anisotrópicos presentan una elevada sección eficaz de absorción y emisión cuando son dopados con iones lantánidos y especialmente para ciertas polarizaciones. Considerando el potencial del Ho y las buenas propiedades de KREW, nuestro trabajo se centra en la investigación de las prestaciones láser en cristales de KREW dopados con Ho utilitzando tanto Tm o Yb como iones sensibilizadores y utilizando fuentes de bombeo emitiendo a 1.9 µm que permiten la excitación directa del nivel emisor. En esta tesis, presentamos los resultados basados en el crecimiento cristalino de monocristales de Ho:KREW, codopajes (Ho,Tm) y (Ho,Yb):KLuW a diferentes concentraciones de Ho, su caracterización en términos de estructura, composición y espectroscopia y finalmente la generación láser alrededor de 2.1 µm. / Eye-safe solid-state lasers that operate in the 2µm spectral range are the subject of interest in the present years because of their potential applications in the field of remote sensing, medicine and as a pump source for Optical Parametric Oscillators (OPOs). Laser transitions around 2 µm are possible in the trivalent lanthanide ions Tm3+ (Tm) (slightly below 2 µm) and Ho3+ (Ho) (slightly above 2 µm). Laser generation in Tm ions is easily achieved with comfortable diode pump sources, however, Ho lasers have usually been achieved in the past either by co-doping the active medium with Tm or by direct pumping of the Ho ions with Tm lasers. Recently, relatively cheap diodes emitting around 1.9 µm are in the market to realize Ho lasers with great potential for power scaling. Ho lasers are more suitable than Tm lasers especially for medical applications because of two reasons: The laser wavelength is slightly above 2µm, where water (main component of human tissue) shows slightly less absorption than the typical wavelength of Tm leading to a deeper penetration in human tissue. The second reason is that Ho lasers can operate in pulsed regime delivering higher energies than Tm lasers due to the longer lifetime of the emitting level 5I7 and medical applications are required to be generally in pulsed regime to avoid thermal damage of human tissue. Many oxide and fluoride crystals were shown to be suitable host for Ho, however little attention was paid to the monoclinic potassium rare earth double tungstate crystal, shortly KRE(WO4)2 or KREW, where RE= Y, Gd, Lu known to be very efficient rare earth solid state hosts for generating intermediate power levels. These anisotropic crystals exhibit very high absorption and emission cross sections when doped with lanthanide ions and especially for selected polarizations. Considering the potentialities of Ho and good properties of KREW, our work focuses in the investigation of the laser performances of a Ho doped KREW either by using Tm or Yb as sensitizers and by using in-band pump sources emitting around 1.9 µm, where the development of compact solid state infrared laser emitting at 2.1 µm for intermediate power levels is followed. Here, in this thesis, we present the results based on growth of single doped Ho:KREW, co-doped (Ho,Tm) and (Ho,Yb):KLuW crystals of several doping concentrations, their characterisation in terms of structure, composition and spectroscopy and finally dedicated for the laser generation around 2.1 µm from these materials, which was highly successful.

L’aréthuse bulbeuse (Arethusa bulbosa L.) est une orchidée tourbicole rare au Québec de par la petite taille de ses populations et les pressions qui pèsent sur son habitat. L’aréthuse est reconnue comme étant intolérante aux changements édaphiques de son habitat, notamment en regard du drainage. Afin de déterminer si l’aréthuse est une bonne espèce indicatrice de l’intégrité écologique des tourbières, cette étude compare des parcelles où l’espèce est présente et où elle est absente. Au cours des étés 2009 et 2010, 37 tourbières du Québec méridional ont été échantillonnées. Des analyses discriminantes ont mis en évidence les facteurs naturels ou d’origine anthropique qui expliquent le mieux la différence entre les quatre types de parcelles. Aussi, la recherche d’espèces indicatrices de la présence de l’aréthuse a été réalisée grâce à la méthode INDVAL. Les résultats montrent que l’aréthuse pousse principalement dans des tourbières présentant des conditions minérotrophes, ce qui est appuyé par le pH élevé et la présence de plantes indicatrices de minérotrophie dans les parcelles contenant l’aréthuse. Cette dernière semble aussi profiter d’une certaine atténuation de la lumière par des arbres dispersés ou par les strates plus basses. Finalement, certaines perturbations de faible ampleur semblent être bénéfiques pour l’aréthuse, ce qui ne permet pas d’affirmer qu’elle est une bonne espèce indicatrice de l’intégrité écologique des tourbières. / Arethusa bulbosa L. is a peatland orchid rare in Québec because of the small size of its populations and the pressures on its habitat. It is known to be intolerant to edaphic changes of its habitat, and particularly to drainage. To determine if A. bulbosa is a good indicator species of the ecological integrity of peatlands, this study compares plots where the species is present from plots where it is absent. During the summers of 2009 and 2010, 37 peatlands were surveyed in southern Québec. Discriminant analyses were performed to find which natural or anthropogenic factors best explain the difference between plots with or without the orchid. Also, indicator species of the presence of A. bulbosa were found using INDVAL analyses. Overall, the results suggest that A. bulbosa was mostly growing in peatlands characterized by minerotrophic conditions. Two evidences supported this point, the high pH values measured and the presence of indicator species of minerotrophy in plots with the orchid. It is likely that A. bulbosa is favored by a certain interception of light by scattered trees or species growing in lower strata. Finally, despite a high floristic quality assessment index (FQAI) in A. bulbosa plots, it is likely that the species takes advantage of small-scale disturbances in it habitat and is therefore not a good indicator species of peatlands ecological integrity.

Les granites à métaux rares ont une faible valeur économique mais sont souvent exploités pour leurs minéraux industriels. L’objectif de ce travail est d’évaluer la potentialité de certains résidus issus de la production de kaolin de St Austell (Angleterre) pour la récupération de métaux critiques (CRMs) comme les Terre Rares légères (LREE), le niobium (Nb), le tungstène (W) et l’étain (Sn) via le développement d’un procédé de récupération des CRMs. L’étude des résidus miniers montre que les CRM sont concentrés dans le résidu micacé avec des teneurs en LREE allant jusqu’à 170 ppm avec 40 à 60% des CRMs distribués dans ce résidu. Un procédé de traitement de ce résidu a été développé incluant des étapes de concentration par gravité et flottation. Les teneurs en LREE permettent la récupération d’environ 60% des LREE avec des teneurs de 1,6 % et 0,5% LREE respectivement dans le concentré de gravité et flottation / Rare metals granites have always been considered of poor economic value due to their low metal grades but, when altered, they are often exploited for their industrial minerals. This work address the recovery of critical metals (CRMs) including Light Rare Earth Elements (LREE) and rare metals (Sn, Nb, W) from St Austell (UK) kaolin residues though the development of a beneficiation process. Results shows that CRMs are pre-concentrated in the micaceous residue stream with LREE grades of 170 ppm, which account from 40% to 60% of the mass of CRM entering the plant. Analysis of this residue streams shows a high variability of CRM grades and suggest a cut-off grades for some of them. A combined gravity/flotation process have been developed for this residue which allow to recover up to 60% LREE with LREE grade of 1.6 to 0.5% for the gravity and flotation concentrate respectively

No description available.

Ce travail de recherche porte sur l'élaboration de céramiques transparentes de CaLa₂S₄ pour la réalisation d'optiques MWIR et LWIR. Différentes méthodes de synthèse de poudres ont été explorées afin d'élaborer des poudres céramiques de grande pureté, cubiques et de morphologie adaptée à la densification. Il en a résulté le développement d'une méthode combustion comme nouvelle voie de synthèse de ce matériau. Différentes techniques de frittage ont été explorées : le SPS, le pressage à chaud (HP) et le frittage sous sulfure d'hydrogène (H₂S) suivi d'un post-frittage HIP. Le pressage à chaud permet d'élaborer des céramiques transparentes dans l'IR. Cependant leurs propriétés optiques sont dégradées par la présence de bandes d'absorption et par un noircissement important dû à l'interaction du matériau avec le graphite. Ces deux problématiques ont été résolues en combinant frittage naturel et compaction isostatique à chaud. La transmission des céramiques obtenues par ce procédé atteint à 13µm la transmission théorique de 68%. / This work focuses on the elaboration of CaLa₂S₄ transparent ceramics for IR optical applications in the MWIR and LWIR atmospheric windows. Various synthesis methods were explored for the elaboration of high purity cubic ceramic powders with adequate morphology for densification. As a result, we developed an innovative combustion method of this material. Different sintering techniques were investigated: Spark Plasma Sintering (SPS), Hot Pressing (HP) and Sintering in sulfurizing atmosphere (H₂S) combined to Hot Isostatic Pressing (HIP). Hot Pressing produces IR transparent ceramics. However, their optical properties are affected by the presence of absorption bands and significant blackening due to the interaction of the material with the graphite. These two issues have been solved by using sintering coupled to post-HIP. Transmission of the optics obtained by this process reaches the theoretical transmission of 68 % at 13μm.

Les composites à matrices céramique (CMC) en raison de leur stabilité à haute température et de leurs propriétés mécaniques sont des matériaux de choix pour remplacer les superalliages à base de nickel au niveau des pièces de turbines. Cependant, les CMC qui sont constitués de carbure de silicium sont sensibles aux espèces oxydantes et corrosives telles que l’eau et l’oxygène à haute température. Le CMC sous cet environnement sévère peut être dégradé chimiquement, s’accompagnant d’un affaiblissement de ses propriétés mécaniques. Pour protéger et augmenter la durée de vie du CMC, un revêtement protecteur (EBC) est déposé généralement par projection thermique. Les céramiques sélectionnées sont des silicates de terres rares. Elles doivent faire face à trois phénomènes majeures :(i) la diffusion des espèces ioniques au sein de la structure cristalline (ii) la réaction de l’eau avec le silicate en surface qui forme des espèces hydroxydes volatiles provoquant la récession du matériau et (iii) la dissolution par les sables présents dans l’atmosphère : les CMAS. Tout l’enjeu de ce travail est dans un premier temps de mettre en place une méthodologie fiable pour caractériser de manière précise et complète l’influence de la microstructure sur les propriétés du matériau. Une deuxième partie sur l’optimisation des performances du matériau a été mise en place en jouant sur l’architecture du revêtement et sa composition. / Ceramic matrix composites due to their high temperature stability and mechanical properties are materials of choice to replace nickel superalloys in turbine. However, CMC are made of silicon carbide which is sensitive to oxidizing and corrosive species such as water and oxygen at high temperature.CMC under this severe environment is chemically degraded and may see its mechanical properties reduced. It seems necessary to cover this CMC by a protective coating : environmental barriers (EBC).These EBCs made of rare earth silicates have to face three most phenomena: (i) diffusion of ionic species in the crystal structures of EBC (ii) the surface volatilization of the silicate induced by reactions with moisture (iii) dissolution by melted sands: CMAS. The aim of this work is to implement amethodology to characterize the influence of the microstructure on the properties of the material. A second part deal with the optimization of the performance of the materials by modifying the architecture of the coating and its composition.

SANTOS, Clenilton Costa dos. Fônons nos sistemas RVO4 e La1-xCexPO4. 2006. 69 f. Dissertação (Mestrado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2006. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2014-11-03T18:45:53Z No. of bitstreams: 1 2006_dis_ccsantos.pdf: 1277913 bytes, checksum: 6a1a955f62dd2dce85a6a88fae471dd9 (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2014-11-03T19:51:52Z (GMT) No. of bitstreams: 1 2006_dis_ccsantos.pdf: 1277913 bytes, checksum: 6a1a955f62dd2dce85a6a88fae471dd9 (MD5) / Made available in DSpace on 2014-11-03T19:51:52Z (GMT). No. of bitstreams: 1 2006_dis_ccsantos.pdf: 1277913 bytes, checksum: 6a1a955f62dd2dce85a6a88fae471dd9 (MD5) Previous issue date: 2006 / In this work we present a Raman investigation of RVO4 (where R = Sm, Ho, Yb and Lu) and La1-xCexPO4 (where x = 0,00, 0,04, 0,16, 0,22, 0,32 and 1,00) compounds. Polarized Raman scattering measurements were carried out in the RVO4 compounds to obtain a better description of the room temperature phonons than those previously reported in literature. We observe that the frequencies of most of phonons increase with increasing atomic number (Z) of R. This behavior results from the lattice contraction when R goes from La to Lu. On the other hand, due to their dimensions and shape, unpolarized Raman scattering was used to investigate the room temperature phonon spectra of La1-xCexPO4 compounds. No appreciable changes were observed, indicating that the LaPO4 lattice is not substantially modified by Ce doping. However, some extra or additional phonons were observed. The origin of these modes comes probably from the activation of infrared modes due to the breakdown of symmetry rules. / Neste trabalho apresentamos uma investigação dos compostos RVO4 (onde R = Sm, Ho, Yb e Lu) e La1-xCexPO4 (onde x = 0,00, 0,04, 0,16, 0,22, 0,32 e 1,00) através da técnica de espalhamento Raman. Medidas de espalhamento Raman polarizadas foram realizadas nos compostos RVO4 para obter uma descrição dos fônons a temperatura ambiente melhor do que aquelas publicadas anteriormente na literatura. Observamos que a freqüência da maioria dos fônons aumenta com o aumento do número atômico (Z) de R. Este comportamento resulta da contração da rede quando R vai de La até Lu. Por outro lado, devido às dimensões e forma dos compostos La1-xCexPO4, medidas de espalhamento Raman não-polarizadas foram usadas para obter seus espectros de fônons a temperatura ambiente. Nenhuma mudança apreciável foi observada, indicando que a rede do composto LaPO4 não sofre modificações consideráveis por causa da dopagem de Ce. Contudo alguns fônons extras ou adicionais foram observados. A origem desses modos advém, provavelmente, da ativação de modos infravermelho causadas por quebras de regras de simetria.

Elabora-se, pela primeira vez, o levantamento e a catalogação descritiva do acervo de livros raros da Universidade de Caxias do Sul com vistas à sua publicização. O trabalho inclui a síntese histórica da Biblioteca Central (BICE/UCS), desde sua fundação, em 1970. Inclui um panorama da estrutura e funcionamento da BICE/UCS e do Sistema de Bibliotecas da UCS (SIBI/UCS). Examina o conceito de raridade bibliográfica e a importância do estabelecimento de critérios de raridade em bibliotecas universitárias. Discute os critérios adotados pela BICE/UCS. / Submitted by Marcelo Teixeira (mvteixeira@ucs.br) on 2014-05-15T16:44:38Z No. of bitstreams: 1 Dissertacao Marcia Carvalho Rodrigues.pdf: 1680433 bytes, checksum: 3cb810d729a8e8068260bac9cc16d5ed (MD5) / Made available in DSpace on 2014-05-15T16:44:39Z (GMT). No. of bitstreams: 1 Dissertacao Marcia Carvalho Rodrigues.pdf: 1680433 bytes, checksum: 3cb810d729a8e8068260bac9cc16d5ed (MD5) / It is elaborated, for the first time, the survey and the descriptive cataloging of the collection of rare books of the University of Caxias do Sul with sights to its publicization. The work includes the historical synthesis of the Central Library (BICE/UCS), since its foundation, in 1970. It includes a panorama of the structure and functioning of the BICE/UCS and the System of Libraries of UCS (SIBI/UCS). It examines the concept of bibliographical rarity and the importance of the establishment of criteria of rarity in university libraries. It argues the criteria adopted for the BICE/UCS.

Elabora-se, pela primeira vez, o levantamento e a catalogação descritiva do acervo de livros raros da Universidade de Caxias do Sul com vistas à sua publicização. O trabalho inclui a síntese histórica da Biblioteca Central (BICE/UCS), desde sua fundação, em 1970. Inclui um panorama da estrutura e funcionamento da BICE/UCS e do Sistema de Bibliotecas da UCS (SIBI/UCS). Examina o conceito de raridade bibliográfica e a importância do estabelecimento de critérios de raridade em bibliotecas universitárias. Discute os critérios adotados pela BICE/UCS. / It is elaborated, for the first time, the survey and the descriptive cataloging of the collection of rare books of the University of Caxias do Sul with sights to its publicization. The work includes the historical synthesis of the Central Library (BICE/UCS), since its foundation, in 1970. It includes a panorama of the structure and functioning of the BICE/UCS and the System of Libraries of UCS (SIBI/UCS). It examines the concept of bibliographical rarity and the importance of the establishment of criteria of rarity in university libraries. It argues the criteria adopted for the BICE/UCS.